1 s2.0 S0169433220331822 Main

Applied Surface Science 541 (2021) 148425
Contents lists available at ScienceDirect
Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc
Stannates, titanates and tantalates modified with carbon and graphene

quantum dots for enhancement of visible-light photocatalytic activity
Marta Paszkiewicz-Gawron a, b, *, Ewa Kowalska b, Maya Endo-Kimura b, Julia Zwara a,
Anna Pancielejko c, Kunlei Wang b, Wojciech Lisowski d, Justyna Łuczak c,
Adriana Zaleska-Medynska a, Ewelina Grabowska-Musiał a
a
Department of Environmental Technology, Faculty of Chemistry, University of Gdańsk, 80-308 Gdańsk, Poland
b
Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan
c
Department of Process Engineering and Chemical Technology, Faculty of Chemistry Gdańsk University of Technology, 80-233 Gdańsk, Poland
d
Institute of Physical Chemistry Polish Academy of Science, 01-244 Warsaw, Poland
A R T I C L E I N F O A B S T R A C T
Keywords: Most efforts in heterogeneous photocatalysis are focused on development of new and stable photoactive mate
Photocatalysis rials efficient in degradation of various pollutants under visible-light irradiation. In this regard, the wide-
Perovskites bandgap perovskite semiconductors, i.e., SrTiO3 (titanate), SrSnO3 (stannate) and AgTaO3 (tantalate), were
Quantum dots
prepared by a solvothermal method, and then modified with carbon quantum dots (CQDs) or graphene quantum
Graphene
Action spectra analysis
dots (GQDs) co-modified with erbium. The photocactivity was investigated for: (i) toluene degradation (gas
Antibacterial properties phase), (ii) phenol decomposition (aqueous phase), and (iii) inactivation of Escherichia coli K12 bacteria. It has
been found that the morphology of semiconductors depends on the synthesis conditions, resulting in the for
mation of spherical particles, rods and faceted particles for SrTiO3, SnSrO3 and AgTaO3, respectively. Addi
tionally, deposition of CQDs and GQDs/erbium has resulted in an enhancement of light harvesting, thus
improved photoactivity under visible-light irradiation. Samples modified with both erbium and GQDs revealed
much higher photoactivity than corresponding pristine and CQDs-modified samples. Moreover, all photocatalyst
modified with GQDs and Er exhibited a significant antibacterial properties under visible light irradiation (λ >
420 nm). Accordingly, it has been proposed that obtained semiconductors modified with QDs and Er are
promising candidates as sustainable, clean and cheap materials for environmental purification under solar
radiation.
1. Introduction photocatalysts for degradation of pollutants as well as for the hydrogen

generation in the reaction of water-splitting [1,2] since the wide
Environmental pollution is one of the most serious problems facing bandgap usually results in high reactivity both for oxidation and
humanity in recent times. Key issues on a global scale include: diffi reduction reactions. Up to now, the most popular photocatalyst, which
culties with access to drinking water, air pollution hampering everyday holds a great potential due to its good chemical stability, high activity,
functioning, as well as over-exploitation of nonrenewable natural re non-toxicity (except toxicity due to the nanomaterial nature) and low-
sources. Human activities are contributing to increasing of environ cost preparation, is titanium(IV) oxide (titania, titanium dioxide,
mental pollution. In this regard, innovative solutions are sought to TiO2) [3]. However, wide bandgap (3.2 eV for anatase) causes also
remove harmful substances from water (polluted water and wastewater) negative consequences , i.e., TiO2 can only be excited by ultraviolent and
and gas phase (polluted air). Among various methods, heterogeneous near-ultraviolent irradiation, which constitutes only about 4% of solar
photocatalysis has been considered as one of the best since under irra light spectrum, and thus visible range of solar spectrum (about 43%)
diation reactive oxygen species (ROS) might be formed with ability to might not be used for photocatalytic reactions. Therefore, it is necessary
decompose efficiently all inorganic and organic compounds even under to design and/or further develop visible-light-active photocatalysts.
natural solar radiation. The wide-bandgap semiconductors are used as Accordingly, it has been proposed that modified perovskites, e.g.,
* Corresponding author.
E-mail address: m.paszkiewicz-gawron@ug.edu.pl (M. Paszkiewicz-Gawron).
https://doi.org/10.1016/j.apsusc.2020.148425
Received 15 August 2020; Received in revised form 7 November 2020; Accepted 8 November 2020
Available online 21 November 2020
0169-4332/© 2020 Published by Elsevier B.V.
M. Paszkiewicz-Gawron et al. Applied Surface Science 541 (2021) 148425
titanates [4,5], stannates [6] and tantalates [7], might be a good alter 2. Materials and methods
native to famous titania photocatalysts, because of their great optical
properties, high photocatalytic activity and good stability. Unfortu All reagents that were used in the experiments were of analytical
nately, most of titanates, stannates and tantalates have bandgap>3.0 eV, purity and used without further purification. Titanium(IV) butoxide
and thus exhibit superlative properties only under UV–Vis irradiation (97%), titanium(IV) chloride (98%), tantalum chloride (99.9%), hex
[8]. Therefore, practical application of above mentioned perovskites is adecyltrimethylammonium bromide (CTAB) (≥98%) from Sigma-
hampered by its low efficiency for utilizing of solar energy resulting in Aldrich (Darmstadt, Germany), strontium nitrate (99%), silver nitrate
high recombination rate of photogenerated charge carries [9,10]. (pure p.a.) from POCh S.A. (Gliwice, Poland), ethylene glycol (99%)
To effectively utilize the sunlight, the narrowing of the band gap of from Chempur (Piekary Śląskie, Poland), sodium hydroxide (pure p.a.)
semiconductors (e.g. titanates, stannates and tantalates) is required to and ethanol (99.8%) from STANLAB Sp. J. (Lublin, Poland) were used
extend its optical absorption range to the visible-light region. Accord for the synthesis of the semiconductors.
ingly, various methods for activation of wide-bandgap semiconductors
towards visible-light response have been explored so far, including 2.1. Preparation of semiconductors: SrTiO3, SrSnO3 and AgTaO3
photosensitization [11], doping with heteroatoms [12], charge transfer
(CT) interaction [13], composite semiconductors’ preparation [14], The wide-bandgap semiconductors, i.e., SrTiO3 (1), SrSnO3 (2) and
modification with noble metals [15], modification with rare-earth ele AgTaO3 (3), were prepared by solvothermal method. (1) SrTiO3: the
ments [16–19], and addition of ionic liquids during the synthesis [20]. titanium(IV) butoxide (TBOT) in an amount of 1.7 g was dissolved in 25
Another, innovative way to improve the photocatalytic activity under mL of ethylene glycol by vigorous stirring for 15 min. In the next step,
visible-light irradiation is the modification with quantum dots (QDs) 10 mL (0.5 M) of Sr(NO3)2 was added dropwise to the solution. Then, 5
[21]. mL of NaOH aqueous solution (5 M) was slowly added under stirring
The QDs-semiconductor materials have attracted interest for their during ca. 10 min. (2) SrSnO3: 2.11 g Sr(NO3)2, 2.79 g SnCl4∙H2O and
unique structural, optical and electronic properties that result from the 0.55 g CTAB were dissolved in 30 mL of water under stirring. Then, the
large surface-to-volume ratio and the quantum confinement effect [22]. mixture was adjusted to pH = 13 with 1 M NaOH. (3) AgTaO3: 0.95 g
The existence of diverse types of QDs presents a further challenge for AgNO3 and 2 g TaCl5 were dissolved in 120 mL of ethylene glycol under
development of various applications since each individual type pos stirring.
sesses unique physicochemical properties. For example, carbon quan The obtained suspensions (1, 2 and 3) were transferred into Teflon-
tum dots (CQDs) have been recently investigated since CQDs are non- lined stainless-steel autoclaves and heated at 180 ◦ C for 24 h. After
toxic, soluble in water and low-cost, as they might be even obtained cooling to room temperature, the precipitates were collected, washed
from glucose, citric acid, chitosan and banana juice [23]. One type of with deionized water and ethanol several times, and dried overnight at
CQDs are graphene quantum dots (GQDs) which have larger content of 60 ◦ C. In the case of SrSnO3 and AgTaO3, the obtained powders were
surface active sites and more accessible edges than graphene sheets calcined at 800 ◦ C for 4 h (temperature rise of 3 ◦ C/min).
[24]. Moreover, they exhibit excellent photostability, high biocompat
ibility, low toxicity and chemical inertness [25]. Therefore, it is expected 2.2. Preparation of quantum dots (GQDs-Er and CQDs)
to increase the photoactivity under visible light irradiation by modifi
cation of titanates, stannates and tantalates by carbon and graphene Graphene QDs were prepared as follows: 2 g of citric acid was heated
QDs. Although, the application for QDs has been rapidly increasing, at 200 ◦ C for 30 min till the colourless citric acid solids turned into or
there is still little known about the photocatalytic use of QDs combined ange liquid. Then, 100 mL of NaOH (10 mg/mL) was added dropwise to
with other materials (e.g., semiconductors). Furthermore, functional the orange liquid under continuous stirring, which was necessary to
ized QDs might be applied for antimicrobial purposes as an alternative keep the solution homogenous. Next, pH value of the solution was
for traditional antibacterial drugs. Some studies on bactericidal prop adjusted to 7 with HCl [38]. Then, the appropriate amount of erbium
erties of CQDs and GQDs have been performed, indicating their ability to (III) nitrate pentahydrate Er(NO3)3⋅6H2O was added to the above
be a bactericidal agent even under visible-light irradiation [26,27]. Only mixture. The molar concentration of erbium was 0.5 mol.%. The solu
a few studies have addresses antimicrobial effects of QDs-modified tion was mixed for 30 min. The prepared GQDs-Er solution was used as
semiconductors [28–33]. stock solution and stored at 4 ◦ C.
Furthermore, additional modification of semiconductors by erbium Carbon QDs were prepared by hydrothermal method. 30 g of citric
ions (besides carbon QDs) may provide the materials with higher ab acid and 30 g of urea were dissolved in 100 mL of deionized water. The
sorption ability and photocatalytic performance [34–36]. Modification obtained solution was transferred into the Teflon-lined stainless steel
of semiconductors with lanthanides (e.g. erbium) has been taken into autoclave and heated at 180 ◦ C for 5 h [39]. After cooling to room
consideration due to their significant role in altering the absorption edge temperature, a brown aqueous solution was obtained. Large particles
of semiconductors, because of the absorption of low-energy photons (up- were removed by centrifugation, and remaining solution with carbon
conversion properties) [37]. The lanthanide ions have strong ability to QDs was used as stock solution.
form complexes with various compounds such as acids, alcohols, alde
hydes and amines through their 4f orbitals. Therefore, various organic 2.3. Preparation of semiconductor-QDs composites
pollutants might be adsorbed on the surface of lanthanide-modified
semiconductors. There is a lack of information about application tita In order to connect QDs with the semiconductor matrix, the physical
nates, stannates and tantalates doped/modified with CQDs-Er for adsorption method followed by calcination was used. Semiconductor
degradation of water pollutants. powder (1.2 g), ethanol (30 mL) and QDs solution (7 mL) were placed in
In view of this, for the first time, a synthesis of highly Vis-photoactive a beaker. The suspension was stirred for 24 h at room temperature with a
stannates, titanates and tantalates modified with CQDs, and GQDs co- magnetic stirrer at a speed of 500 rpm. Then, the samples were dried at
modified with erbium (0.5 mol.%) has been performed. The effect of 60 ◦ C and calcined at 300 ◦ C for 1 h.
the QDs and Er on the structural and optical properties, and the pho
tocatalytic activity of SrTiO3, AgTaO3 and SrSnO3 has been investigated 2.4. Characterization of the photocatalysts
for both degradation of chemical and microbiological pollutants.
The crystalline structures and lattice parameters of the prepared
samples were confirmed by X-ray diffractometer Rigaku MiniFlex 600
(Rigaku, The Woodlands, TX, USA) system equipped with a copper
2
target. The morphology of SrTiO3 semiconductors was analysed by 2.6. Measurement of photocatalytic activity for phenol degradation in an
scanning electron microscopy (SEM) using a Hitachi Microscope aqueous phase– Action spectra (AS) analysis
HD2000, as well as transmission electron microscopy (STEM-EDX, FEI
Europe, model TecnaiF20 X-Twin). Measurement of absorption prop The action spectra (AS) analyses for phenol degradation in an
erties (diffuse reflectance spectra, DRS) was performed with the Shi aqueous phase were also conducted. Photocatalyst powder (15 mg) was
madzu MSP-2450 spectrometer equipped with an integrating sphere, suspended in an aqueous solution (3.0 mL) containing phenol (C0 = 20
and BaSO4 was used as a reference. Measurement of photoluminescence mg∙L− 1) and placed in a rectangular quartz cell (10 mm square and 50
properties (fluorescence spectra) was completed with the HITACHI F- mm in height), then irradiated at monochromatic wavelengths for 60
4500 spectrometer. The surface composition was analysed by X-ray min using a diffraction grating-type illuminator (Jasco, CRM-FD)
photoelectron spectroscopy (XPS) using a PHI 5000 VersaProbe equipped with a 300-W xenon lamp (Hamamatsu, C2578-02). The
(ULVAC-PHI) spectrometer with monochromatic Al Kα irradiation (hν = light intensity was measured by an optical power meter (HIOKI 3664).
1486.6 eV) from an X-ray source operating at 100 μm spot size, 25 W and During the experiments, the suspension was continuously stirred, and a
15 kV. The “as prepared” semiconductors were analyzed using a modi portion (0.2 mL) of the reaction mixture was withdrawn every 20 min
fied PREVAC [https://www.prevac.eu/en/2,offer/36,sample-holders,3. with a syringe, filtered by a syringe filter (∅ = 0.2 μm, Whatman, Mini-
html] sample holder (standard sample holder equipped with a plate UniPrep) to remove photocatalyst particles, and injected to high-
adaptor of powder holding containing a cylinder pocket, 3 mm diameter, performance liquid chromatograph (HPLC). The HPLC system was
1 mm depth). The high-resolution (HR) XPS spectra were recorded with equipped with a WAKOSIL-II SC18 AR reversed-phase column (250 ×
the hemispherical analyser at the pass energy of 23.5 eV, the energy step 4.6 mm) with a mobile phase of acetonitrile (29.5%), water (70%) and
of 0.1 eV and the photoelectron angle of 45◦ with respect to the surface phosphoric acid (0.5%), and analysis parameters were fixed at 1 mL
plane. Charge compensation was achieved using a PHI’s patented dual min− 1 of a flow rate and UV detector at 254 nm.
beam charge neutralization system [40]. Casa XPS software was used to
evaluate the XPS data. The binding energy (BE) scale of all detected 2.7. Antimicrobial properties
spectra was referenced by setting the BE of C 1 s signal to 284.8 eV. The
BET (Brunauer–Emmett–Teller) surface area and pore size of the pho Pristine and modified semiconductors (50 mg) were dispersed in 5
tocatalysts were measured by a QuantaChrome Instruments, 6AG/HOB. cm3 Escherichia coli (E. coli) K12 ATCC29425 suspension in a sterile
All samples were degassed at 200 ◦ C prior to nitrogen adsorption mea sodium chloride aqueous solution (8.5 g dm− 3) in a glass test tube, and
surements. The BET surface area was determined by the multipoint irradiated by a xenon lamp (CX-04E, Eagle Engineering, Ltd., Japan)
method using the adsorption data in the relative pressure (P/P0) range of equipped with cut-off filter (λ > 420 nm) and a cold mirror in thermo
0.05–0.3. The Raman spectra were measured with a Thermo Scientific stated water bath under continuous stirring (using a magnetic stirrer at
DXR Smart Raman spectrometer with a 532 nm laser as the excitation speed of 500 rpm) at 25 ◦ C. The distance between the solution and the
source under ambient conditions. Fourier-transform infrared spectros light source was fixed at ca. 15 cm. The radiant flux was monitored with
copy (FTIR) analysis was performed on Nicolet iS10 FTIR spectrometer a spectroradiometer (USHIO, USR-45) and equaled to 20.0 mW cm− 2.
in the scan range of 500–4000 cm− 1 as the diffuse reflectance for powder The process was carried out for 3 h for each sample. Samples were
samples (by rarefying 5% of the photocatalysts in KBr) and by ATR mode collected at 0.5, 1.0, 2.0 and 3.0 h. The content of photocatalyst and
for liquid sample of pristine CQDs and GQDs with a resolution of 8 cm− 1 bacteria was adjusted, according to the previous findings [42]. The
at room temperature. control experiments in darkness and for NaCl solution were also per
formed. Serial dilutions (10-1 to 10-6) were prepared in saline solution
2.5. Measurement of photocatalytic activity for toluene degradation in a (0.85%). The samples were placed on Plate Count Agar (Becton, Dick
gas phase inson and Company, Franklin Lakes, NJ, USA), the plates were incubated
for 20 h at 37 ◦ C (ETTAS EI-450B incubator), and then the colony
Photocatalytic activity of the prepared samples was determined in forming unit (CFU × cm− 3) was calculated. The procedure for deter
the process of air cleaning from volatile organic compounds (VOC). mining antibacterial activity is shown schematically in Fig. 1.
Toluene was used as a model air contaminant. The photocatalytic ac
tivity tests were carried out in a flat stainless steel reactor (30 cm3) [41]. 3. Results and discussion
The reactor was equipped with a quartz window, tow valves and septa.
An array of 25 LEDs (λmax = 415 nm, 63 mW per diode) was used as an Solvothermal synthesis performed at 180 ◦ C was applied for prepa
irradiation source. Measured light flux (in the range from 400 to 430 ration of three types of perovskites, namely SrTiO3, SrSnO3 and AgTaO3.
nm) was 10.5 mW cm− 2 (Hamamatsu, Japan UV Power meter, model The materials were then modified with CQDs, and with GQDs co-
C9536-01). Glass plate (20 mm × 20 mm) coated with the layer of modified with erbium ions. Firstly, formation of graphene and carbon
photocatalyst was placed at the bottom of the reactor, followed by QD was confirmed by UV–Vis absorption and fluorescence spectroscopy.
closing the reactor with quartz window. Subsequently, the gas mixture Then, the modified perovskites were analysed in respect to the crystal
was passed through the reaction space for 1 min. After closing the structure, morphology, optical and surface properties and the photo
valves, the reactor was kept in dark for 30 min to achieve adsorption/ catalytic activity, as discussed below.
desorption equilibrium. A reference sample was taken just before
starting irradiation. The analysis of toluene concentration in the gas 3.1. Characteristics of GQDs-Er and CQDs
phase was performed using gas chromatograph (SCHIMADZU, GC 2010)
equipped with flame ionization detector (FID) and Phenomenex capil The optical properties of GQDs were investigated by UV–Vis ab
lary column (30 mm × 25 mm, 0.5 µm). The samples (200 µL) were sorption and fluorescence spectroscopy (Fig. 2). The absorption peak at
dosed with a syringe. Helium was used as a carrier gas (1 mL min− 1). To 365 nm (Fig. 2a) correlates well with π-π* transition of C–
– C [43]. The
estimate toluene loss due to adsorption on the photocatalyst surface, the maximal emission was detected at ca. 465 nm, independently on the
experiments in dark were also proceeded, where ca. 12% decrease in excitation wavelength, revealing excitation-independent fluorescent
toluene concentration was obtained. properties, as previously reported [38]. It means that the emission
wavelength of GQDs was stable, with the excitation wavelength ranging
from 350 to 400 nm (Fig. 2b). The photograph of the obtained solution
taken under 395 nm LED irradiation (Fig. 2c (left)) confirms the blue
fluorescence of GQDs (no emission for irradiated water (Fig. 2c (right)),
3
Fig. 1. Scheme of antibacterial assay against E. coli procedure.
Fig. 2. Optical properties of GQDs_Er: (a) UV–Vis absorption spectrum; (b) fluorescence excitation and emission spectra; and (c) photographs under UV irradiation
for: GQDs (left) and water as a reference sample (right).
Fig. 3. Optical properties of CQDs: (a) UV–Vis absorption; (b) fluorescence excitation and emission spectra; (c) picture under UV irradiation of carbon quantum
dots (CQDs).
4
which is consistent with the spectrum shown in Fig. 2b (excitation with authors said that the upconversion fluorescence has been often cited as
UV irradiation gives the emission in the visible irradiation range). Peaks an important feature in carbon nanodots (CNDs) and graphene quantum
indicating the erbium content were not noticeable in the spectrum dots (GQDs); and some mechanisms and potential applications have
probably because of too low content of this element in the tested sam been proposed. Contrary to such a general belief, they demonstrated in
ples. The presence of erbium in the samples was confirmed by other this report no observable upconversion fluorescence based on five
techniques, which is discussed later in the article. different synthesized CNDs and GQDs. They confirmed that the so-called
Carbon QDs showed absorption under the visible range of irradiation upconversion fluorescence actually originates from the normal fluores
from 430 to 500 nm and at 650 nm (Fig. 3a). The first peak might cence excited by the leaking component from the second diffraction in
originate from π-π* transition of C– – C [43]. The phenomenon of the the monochromator of the fluorescence spectrophotometer. Upconver
second wide peak (at 650 nm) is presumably related to the presence of sion fluorescence can be identified by measuring the excitation intensity
carbon dots dispersed in the solution, as also observed by other scientific dependence of the fluorescence [52]. Also in the following article, the
groups. For comparison, Li et al. observed a well-defined, strong ab authors deny the up-conversion properties of CQDs (the title of that
sorption band at about 700 nm for carbon nanodots prepared via hy paper is: A misunderstanding about upconversion luminescence of car
drothermal method from citric acid and urea [44]. Wang et al. noticed bon quantum dots) [53].
the absorption peak at 530 nm from CQDs, claiming that it indicated the
high conjugation and high quality of CQDs [45]. The photoluminescence
(PL) spectra, shown in Fig. 3b, indicate that CQDs emit in blue and green 3.2. Characteristics of semiconductor-QDs samples
ranges, depending on the excitation wavelengths, i.e., PL from nearly
450 to 550 nm after excitation at 300–500 nm, respectively. The bath 3.2.1. The XRD and BET analyses
ochromic shift in the emission wavelength correlates with excitation The XRD patterns of the pristine and modified samples are shown in
wavelengths, i.e., the longer excitation wavelength is, the longer is the Fig. 4. It is clear that all diffraction peaks of pristine SrTiO3, indexed to
emission wavelength. It should be pointed out that such spectra are cubic crystal system, are observed at near 22.8◦ , 32.4◦ , 40.1◦ , 46.6◦ ,
typical for CQDs [46,47]. The maximum photoluminescence intensity 50.1◦ , 57.8◦ , 67.9◦ , and 77.1◦ , as presented in Fig. 4a. Characteristic
with emission at 450 nm was observed when CQDs were excited at 400 peaks of trigonal AgTaO3 are noticed at ca. 22.9◦ , 32.3◦ , 46.1◦ , 54.1◦ ,
nm. The broad emission bands revealed the complex mechanism of the 57.6◦ , 67.7◦ and 76.8◦ (see Fig. 4b) for both pristine and modified
CQDs photoluminescence [48], as already reported [49,50]. samples. However, additional peaks have also been detected, such as
Both types of QDs (graphene with erbium and carbon) did not Ag2Ta4O11 and Ta2O5 (Fig. 4b). The additional peaks corresponding to
revealed the up-conversion properties, i.e., they could not emit ligth at Ta2O5 and Ag2Ta4O11 observed in Fig. 4b might come due to occur
shorter wavelenghts (e.g., UV) after absorption of light at longer additional side reactions. We assume that much more drastic cleaning
wavelenghts (i.e., Vis or NIR). It should be pointed that the addition of and calcination conditions (such as different in properties cleaning so
0.5% erbium did not cause the appearance of up-conversion. Never lutions, higher pressure and temperature) could completely remove the
theless, decorating the semiconductors with GQDs/Er3+ and CQDs has rest compounds. For the AgTaO3_GQDs_Er sample we found an intensive
increased the photocatalytic activity, as discussed in detail in the further peak at around 39◦ ascribed to a metallic silver (1 1 1) [54–57]. We
sections of this article. suspected that it might be a result of the synthesis conditions and
In case of carbon quantum dots the up-conversion fluorescence are coexistence of two metals, silver and erbium. The remaining charac
frequently cited as an important feature. However we can find in the teristic peaks for metallic silver (i. e. (2 0 0) at around 44.3◦ , (2 2 0) near
literature many examples of contradicting this thesis. Many research 64.5◦ and (1 3 1) 77.4◦ coincide with that one’s corresponding to
groups obtained carbon QDs which couldn’t exhibit the transformation AgTaO3 were observed [54–57].
of visible light (or NIR) to UV light [44,45,47,49,51]. Additionally, very The diffraction patterns, assigned to orthorhombic SrSnO3 with
interesting article was published in Chemical Communications [52]. The peaks at ca. 22.1◦ , 25.3◦ , 31.5◦ , 36.7◦ , 45.0◦ , 50.7◦ , 52.1◦ , 55.9◦ , 65.5◦ ,
66.4◦ , 70.0◦ and 74.4◦ , are presented in Fig. 4c. The average crystalize
Fig. 4. XRD patterns of the pristine and modified samples of: (a) SrTiO3; (b) AgTaO3; (c) SrSnO3.
5
sizes calculated using Scherrer equation were equalled to 32.5, 20.1 and
8.81 nm for AgTaO3, SrSnO3 and SrTiO3, respectively. Furthermore, the
addition of quantum dots to the reaction environment resulted in sig
nificant changes in crystallize sizes. The refined lattice parameters a, b
and c as well as cell volume are summarized in Table 1. The influence of
CQDs and GQDs/Er3+, for both SrTiO3 and AgTaO3 samples led to a
decrease in the average crystallize sizes, from 8.4 nm to 8.0 and 3.6 for
pristine sample, SrTiO3_CQD and SrTiO3_GQDs_Er, respectively, and
from 32.5 nm to 23.1 and 16.5 nm, for pristine sample, AgTaO3_CQDs
and AgTaO3_GQDs_Er, respectively. On the other hand, the increase in
the crystallize sizes after addition of quantum dots to SrSnO3 was
observed, i.e., from 20.9 nm for pristine sample to 28.9 and 24.5 nm for
SrSnO3_CQDs and SrSnO3_GQDs_Er, respectively. Accordingly, it has
been proposed that the second calcination used for preparation of the
QDs-composites caused further growth of SrSnO3 crystallites. However,
in the case of SrTiO3 and AgTaO3 composites an opposite effect was
observed. Therefore, it might be assumed that the initial presence of the
amorphous phase in both pristine semiconductors is a reason of this
phenomenon, i.e., during their crystallization fine NPs are formed, and
thus the resultant sizes (average/mean) are smaller after second calci
nation (higher crystallinity of samples). The specific surface areas of as-
prepared samples, calculated based on the BET isotherms, are listed in
Table 1. The results clearly showed that the addition of quantum dots to
the reaction environment led to decrease in the specific surface area,
probably because of the pore blocking by QDs. Similar results have
already been reported by Stengl et al. for TiO2-graphene nanocomposite
[58]. They reported that the increase of graphene nanosheets content in
the nanocomposite led to the decrease of the specific surface area.
3.2.2. Morphology
The morphological properties of GQDs/Er-modified perovskites
(AgTaO3, SrSnO3 and SrTiO3) were studied by SEM and TEM analyses
(Fig. 5). It was found that AgTaO3_GQDs_Er formed faceted particles
with width and length of ca. 300 and 870 nm, respectively (Fig. 5a). It is
worth to noticed that each of the crystals consisted of several over
lapping thin layers of 4–8 nm thickness and irregularly shaped particles
of about 4–15 nm on the surface. (Fig. 5b–c). These irregular particles
suggest the presence of GQDs on the surface of the perovskite. The
enlarged image (Fig. 5d) of AgTaO3_GQDs_Er revealed the longitudinal
rods/sheets of about 1 nm thickness, indicating the presence of gra
phene. The typical images of SrSnO3, i.e., in the form of porous rods with
a length of 3–10 µm and a diameter from 0.5 to 1.5 µm, are shown in
Fig. 5e–f. Kim et al. reported the synthesis of SrSnO3 particles of similar
morphology i.e., rod-like particles with a square base of 0.7–1.5 µm and Fig. 5. STEM images of the prepared samples: AgTaO3_GQDs_Er: SEM (a) and
a height of approximately 2.0–3.0 µm [59]. The differences in the size TEM (b-d) images; SrSnO3_GQDs_Er: TEM (e) and SEM (f) images,
might result from the different preparation routes than that in our ex SrTiO3_GQDs_Er: SEM (g-h) images; and SrSnO3_CQDs: SEM (i-j).
periments (different precursor - SrCl2∙6H2O, hydrothermal reaction at
200 ◦ C for 18 h, calcination at 600 ◦ C for 6 h). SEM images for SrTiO3 edge could be observed on their surface. Unfortunately, in all obtained
(Fig. 5g-h) revealed the presence of particles with a size from 300 to 800 semiconductors it is difficult to indicate (on the basis of SEM and TEM)
nm. What is more, they were highly aggregated, which is in line with our the presence of erbium on the surface of perovskites, due to its low
previous studies [5]. These particles consisted of thin petals with an content in the samples.
average thickness of about 10 nm. Moreover, non-uniform jagged at the
Table 1
Crystallographic properties and BET area of the obtained samples.
Sample label Type of QDs Crystallite size (Å) Cell parameters (Å) Cell volume (Å3) BET surface area [m2∙g− 1]
a=b c
SrTiO3 – 84 3.8990 3.8990 59.273 107.9

SrTiO3_CQDs C 80 106.8
SrTiO3_GQDs_Er G 36 82.95
AgTaO3 – 325 5.5281 13.7159 363.00 0.91
AgTaO3_CQDs C 231 0.74
AgTaO3_GQDs_Er G 165 0.83
SrSnO3 – 209 5.5281 8.0640 262.643 13.7
SnSrO3_CQDs C 289 8.45
SnSrO3_GQDs_Er G 245 8.45
6
In addition, EDS mapping was carried out for three selected samples sodium originated from precursors used in the preparation process
(SrSnO3_GQDs_Er, AgTaO3_GQDs_Er, SrSnO3_CQDs) to confirm the (Table 2), which might also contributed to an increase in the fraction of
presence of QDs (Fig. 6). The EDS analysis confirmed the presence of C4 (Na2CO3) [60]. Moreover, it should be pointed out that all samples
signals from C, Sr, Sn, Ta and Ag from the above-mentioned composites. might be partially covered with the carbon-like compounds, being
formed as a result of exposition to air after their preparation. However,
3.2.3. The XPS analysis evaluation of this effect is rather doubtful, because both the specific
The elemental composition of the surface of pristine and modified surface area and the chemical composition of pristine samples was found
SrTiO3, AgTaO3, SrSnO3 was determined by XPS, and results are to be changed as a result of CQDc and GQDs_Er modification. The C1
collected in Table 2. The chemical character of elements in the SrTiO3, fraction of contributed carbon species was evidently largest in all pris
AgTaO3 and SrSnO3 samples was identified in HR XPS spectra, presented tine samples (Table 3).
in Fig. 7, Fig. 8 and Fig. 9, respectively. In the case of SrTiO3 (Fig. 7), two
states of strontium in Sr 3d spectra, i.e., Sr 3d5/2 peaks at 132.8 and 3.2.4. The FTIR and Raman analyses of lattice vibration modes
133.6 eV, were assigned to SrTiO3 and SrCO3 species, respectively [60], Interfered spectra of the obtained samples are presented in Fig. 10.
and the Ti 2p3/2 signals, located at 458.3 eV and 456.7 eV, are charac The strongest signal, centred at around 590 cm− 1, corresponds to
teristic for SrTiO3 and Ti3+species, respectively [60–62]. The AgTaO3 characteristic stretching vibrations of Sr-Ti-O, and thus confirming the
samples were identified by Ag 3d and Ta 4f spectra (Fig. 8). The Ag 3d5/2 successful synthesis of SrTiO3 (Fig. 10a). The bands in the range of
peak at 368.0 eV described well the pristine AgTaO3 and the main Ta 4f 2700–2900 cm− 1 were assigned to the presence of CH3 and CH2 sym
signals (Ta 4f7/2 close to 26.0 eV) identify the AgTaO3 compounds [63]. metric vibrations in the alkyl chain, originated from the precursor
The SrSnO3 composites were well characterized by the Sr 3d and Sn 3d (TBOT), and for the modified samples were concealed. Pristine SrTiO3 in
spectra (Fig. 9). The Sr 3d5/2 signals at 132.7 and 133.7 eV, indicated comparison with modified samples exhibited the same features but
two states of strontium assigned to SrSnO3 and SrCO3, respectively transmittance was less intense. The functional groups corresponding to
[60,64], and the Sn 3d5/2 signal located at 486.3 eV is attributed to the Ag–O bonds were noticed at around 690 and 820 cm− 1 (Fig. 10b).
SrSnO3 [64]. The successful erbium doping is confirmed by Er 4d spectra For SrSnO3, the vibrations associated to Sn–O molecular vibrations
recorded for all samples containing graphene QDs and erbium. How were observed at 400–850 cm− 1. The peaks appearing at 480 and 762
ever, for SrTiO3_GQDs_Er and SrSnO3_GQDs_Er samples, the Er 4d cm− 1 correspond to vibrations of the O–Sn–O bridging (Fig. 10c).
spectra were partially overlapped with Sr-loss peaks (see Fig. 7 and Besides the bands originated from metal-oxygen, in each series of the
Fig. 9). samples, the bands located in the range of 3100–3700 cm− 1 and
To confirm effective modification of SrTiO3, AgTaO3 and SrSnO3 2600–2700 cm− 1, originated from hydroxyl groups vibration, and the
with CQDs and GQDs, the C 1 s spectra were analysed for all samples. bands centred around 1600–1700 cm− 1 were associated with O-H
The deconvoluted C 1s spectra revealed four fractions, denoted as C1- deformation vibrations, originated from the water adsorption on the
C4, and corresponding to C1 – C–C bonds; C2 – C–O; C3 – C–Cl/ surface of the samples. It is worth to note that the bands corresponding
C–– O; C4 – O–C– – O/Na2CO3 (Table 3). Accordingly, it was found that to both types of QDs, might be distinguished at around 1620–1750 cm− 1
the C4 fraction was higher in all modified samples than that in pristine and 1470 cm− 1 (see Fig. 10d). However, it is hard to distinguish the
semiconductors. Moreover, the ratio (C3 + C4)/(C1 + C2), representing presence of CQDs and GQDs with Er ions in modified samples in com
the relative carbon fraction distribution, evidently was higher in carbon- parison with the pristine ones due to overlapping of the bands. It has
containing samples (Table 3). However, it should be noted, that all been assumed that the differences in the intensities might result from the
samples co-modified with GQDs and Er contained significant amount of preparation routes of the composites.
Fig. 6. STEM/EDS mapping for three selected samples: (a) SrSnO3_GQDs_Er, (b) AgTaO3_GQDs_Er, (c) SrSnO3_CQDs.
7
Table 2
Elemental contents in the surface layer of pristine SrTiO3, AgTaO3 and SrSnO3 composites and the samples doped by carbon quantum dots (CQDs) as well as graphene
quantum dots and erbium (GQDs_Er).
Sample label Ag cont. at.% Ta cont. at.% Sr cont.at.% Ti cont. at.% Sn cont. at.% O cont. at.% Er cont. at.% C cont. at.% Other
(Na, Cl,) cont. at.%
SrTiO3 – – 21.24 13.76 – 52.00 – 13.00 <0.1

SrTiO3_CQDs – – 22.90 14.65 – 57.41 – 5.04 <0.1
SrTiO3_GQDs_Er – – 15.84 9.48 – 47.42 0.11 9.75 17.40
AgTaO3 15.56 15.06 – – – 30.09 – 24.55 14.74
AgTaO3_CQDs 18.89 10.76 – – – 21.34 – 29.99 19.02
AgTaO3_GQDs_Er 3.71 4.26 – – – 33.05 0.98 36.34 21.66
SrSnO3 – – 16.12 – 16.45 54.76 – 12.67 <0.1
SrSnO3_CQDs – – 18.72 – 15.07 54.79 – 11.42 <0.1
SrSnO3_GQDs_Er – – 16.62 – 2.64 46.42 0.39 20.06 13.87
Fig. 7. High resolution XPS spectra of C 1s, O 1s, Sr 3d, Ti 2p, Er 4d collected on the surface of pristine and modified SrTiO3 samples.
Fig. 11 represents three Raman spectra denoted as a–c and corre spectrum of pristine SrSnO3 demonstrated main signals, attributed to the
sponding to the obtained semiconductors, i.e., SrTiO3, AgTaO3 and movement of Sn-O-Sn groups, at 221 and 266 cm− 1. The band at 559
SrSnO3, respectively. Characteristic bands related to the typical vibra cm− 1, associated with Sn–O stretching motions, has already been re
tional modes of the as-prepared perovskites associated with metal- ported for SrSnO3 [69–71]. The spectrum analysis revealed the presence
oxygen interaction were observed (below 600 cm− 1 for Sr–O, at of two peaks located in the range of 1380–1580 cm− 1, associated with
around 690 and 820 cm− 1 for Ag–O and at 559 cm− 1 for Sn–O, graphene QDs, as presented in Fig. 11c. However, analysis of
respectively). For example, several broad bands observed in the fre SrSnO3_CQDs was hard to employ, probably because of the strong
quency range up to 600 cm− 1 might be associated with different modes reflection from the laser beam and fluorescence phenomenon preventing
of O–Sr–O and Sr-Ti–O (see Fig. 11a). These structures arose at about the measurement. Moreover, the peaks at 279, 700 and 1073 cm− 1 could
134, 175, 257 and 590 cm− 1 for pristine as well as modified SrTiO3 indicate SrCO3, as reported previously [72].
samples [65]. Furthermore, in the case of the SrTiO3_CQDs and
SrTiO3_GQDs_Er samples, two additional peaks at around 1340 and 3.2.5. Photoluminescence properties
1580 cm− 1 were observed [66,67], probably associated with the pres The PL emission spectra of all samples were analysed in the wave
ence of carbon and graphene quantum dots on the surface of SrTiO3. As length range of 350 – 700 nm, as presented in Fig. 12. All pristine
expected, the similar bands corresponding to carbon and QDs at around samples exhibited the highest PL intensity what suggests the highest
1470 and 1620 cm− 1 were also noticed for the modified AgTaO3 samples efficiency of charge carriers’ recombination. A peak at around 398 nm is
(Fig. 11b). Although, different intensity of signal was noticed for the attributed to the emission of band gap transition, originated from the
AgTaO3_GQDs_Er and AgTaO3_CQDs samples, the same features were recombination of photoexcited electron-hole pairs. The emission bands
observed. The spectrum of pristine AgTaO3 is consistent with previous at around 422, 444 and 463 nm are attributed to presence of O●- 2 va
literature reports, where the functional groups corresponding to the Ag- cancies. The oxygen vacancies correspond to photoinduced charge traps
O bonds were noticed at around 690 and 820 cm− 1 [68]. The Raman and adsorption sites, resulting in hindering of the electron-hole
8
Fig. 8. High resolution XPS spectra of C 1s, O 1s, Ag 3d, Ta 4f, Er 4d collected on the surface of pristine and modified AgTaO3 samples.
Fig. 9. High resolution XPS spectra of C 1s, O 1s, Sr 3d, Sn 3d, Er 4d collected on the surface of pristine and modified SrSnO3 samples.
recombination and thus, enhancement of the photocatalytic activity results for SrTiO3 samples were observed by Umar et al. [74].
[73]. The peak at about 525 nm is attributed to the radiative recombi
nation of mobile electrons with trapped holes. The lowest PL intensity 3.2.6. Photocatalytic activity for toluene degradation in the gas phase
was observed for the samples decorated with GQDs. The observation of The photocatalytic activity of the prepared samples was evaluated
the sharp and intensive PL emission spectra for SrSnO3_GQDs_Er, for toluene degradation, and the obtained results are shown in Fig. 13.
AgTaO3_CQDs and AgTaO3_GQDs_Er was difficult to notice. Similar First, the blank test without photocatalyst was performed to check the
9
Table 3 erbium ion doping since erbium ion can lead to the red shifts of optical
The analysis of C 1 s XPS spectra of pristine AgTaO3, SrTiO3 and SrSnO3 com adsorption edges which enhanced degradation process. Moreover, it
posites and the samples doped by carbon quantum dots (CQDs) as well as gra might be expected that the excited electrons reduce the surface Er3+ to
phene quantum dots and erbium (GQDs_Er). Er2+ upon irradiation. It is worth to mention that those composites have
Sample label C 1 s fraction (%) higher photocatalytic efficiency despite lower specific surface area in
C1 C2 C3 C4 (C3 + comparison with pristine perovskites.
C4)/(C1
C–C C–O –C–Cl/ O–C– –O/
284.8 286.3 C–
–O Na2CO3
+ C2) 3.2.7. Photocatalytic activity for phenol degradation in the liquid phase –
eV ± 0.5 287.9 ± 289.4 ± Action spectra
eV 0.4 eV 0.3 eV The action spectrum analysis of phenol photodegradation was per
SrTiO3 49.67 32.76 0 17.57 0.21 formed by estimation of the apparent quantum efficiency (AQE) in
SrTiO3_CQDs 24.03 13.57 0 62.40 1.66 dependence of irradiation wavelengths (380–600 nm). The AQE was
SrTiO3_GQDs_Er 14.14 4.33 0 81.53** 4.41** calculated as the ratio of the rate of the electron consumption from the
AgTaO3 64.97 23.98 8.41* 2.63 0.12* initial rate of benzoquinone (first product of the phenol oxidation) for
AgTaO3_CQDs 53.81 21.31 21.89* 0 0.29*
AgTaO3_GQDs_Er 53.43 10.06 11.44* 25.07** 0.58*/**
mation to the flux of the incident photons for pristine and modified
SrSnO3 57.79 4.20 0 38.01 0.61 SrTiO3 and AgTaO3 semiconductors. In the case of pristine and modified
SrSnO3_CQDs 46.80 14.40 0 38.81 0.63 SrSnO3, the AQE was estimated on the basis of the initial rates of 1,2,4-
SrSnO3_GQDs_Er 11.71 3.24 0 85.05** 5.69** benzenetriol formation, which is one of the subsequent products of the
*
C-Cl. phenol decomposition (after benzoquinone) since benzoquinone was
**
C-Na. oxidized fast (after 20 min of irradiation) into subsequent phenol
decomposition products [75]. It was found that AQE values of the
direct photolysis of toluene, and ca. 12% of toluene was decomposed in modified samples were much higher than that of the pristine samples for
such conditions. All pristine samples (SrSnO3, SrTiO3 and AgTaO3) were all semiconductors (SrTiO3, SrSnO3 and AgTaO3), as shown in in Fig. 14.
the least active, showing toluene degradation of 13%, 26% and 14%, Moreover, similar to toluene degradation, samples modified with GQDs
respectively. The photoactivity significantly increased (five, two and and erbium were more active than those with CQDs. Two possibilities of
four times, respectively) after samples’ modification with GQDs an Er, higher photoactivity of GQDs/Er-modified samples could be considered,
reaching the degradation efficiency of 67%, 48% and 57%, respectively. i.e., (i) graphene morphology/properties of carbon or (ii) the erbium
Whereas, the activity enhancement was much lower (3.2, 1.3 and 1.9 presence. It has been reported that graphene could activate titania to
times, respectively) after samples’ modification with CQDs, reaching wards Vis response, as electrons could migrate from photoexcited state
41.3%, 34.1% and 26.1%, respectively. The observed photocatalytic of graphene to CB of titania. For example, Wang et al. showed Vis-
enhancement of SrSnO3_GQDs_Er, SrTiO3_GQDs_Er and response of both carbon and carbon/graphene modified titania for
AgTaO3_GQDs_Er composites might be attributed to the presence of phenol degradation, but it was found that co-presence of graphene could
Fig. 10. FTIR analysis of pristine and modified samples of: (a) SrTiO3; (b) AgTaO3; (c) SrSnO3 and (d) pure carbon and graphene quantum dots.
10
Fig. 11. Raman spectra of pristine and modified samples of: (a) SrTiO3; (b) AgTaO3; (c) SrSnO3.
hindered Vis-activity of carbon-modified samples [76]. Castaneda- trap photogenerated electrons from SrTiO3/SrSnO3/AgTaO3 and pro
Contreras et al. attributed the sensitization of titania to visible-light mote the separation of photogenerated electron-hole pairs (which is
response (a red shift in the band-gap) due to the addition of erbium confirmed by PL measurement) [79]. Additionally, literature reports
ions [77]. They proposed that Er ions could transform visible light into state that lanthanides can also form complexes with various Lewis bases,
UV light (up-conversion) to excite the wide band-gap semiconductor e.g., acids, amines, aldehydes, alcohols and thiols, by the interaction of
(TiO2). Although, the bathochromic shift and up-conversion process listed functional groups with the f-orbitals of the lanthanides [34].
have not been noticed in the present study but the improved photo Therefore, inter-corporation of erbium ions in the semiconductor’s
catalytic activity is obvious, what has also been observed in the litera matrix could provide capabilities to concentrate the organic pollutants
ture [17–19]. It should be pointed out that the characteristic absorption at the samples surface [19].
bands for erbium in the third oxidation state at 475, 524 and 655 nm Although, the action spectra do not resemble exactly the respective
[18] were not detected in this study, probably due to small content of absorption spectra (Fig. 14 a, b, c), the response under visible-light
erbium in the samples, the XPS data (Table 2 and on the HR spectra irradiation confirms Vis activity of the modified samples. It should be
performed for erbium modified samples – Figures: 7, 8 and 9) confirm pointed out that “absorption spectra” were taken as diffuse reflectance
the erbium presence. Therefore, the possible excitation of semi spectra, and thus scattering on large particles of photocatalysts, espe
conductors by erbium could not be excluded. In such case, it is highly cially at longer wavelengths was also included in these spectra. In the
possible that GQDs could capture the excited electrons, and thus reduce case of modified SrTiO3 and SrSnO3 samples, the Vis response was
the recombination of electron-hole pairs [78]. It is well known that observed in the range from 400 nm to 540 nm. In contrast, modified
electron-hole separation is one of the key factors limiting the efficiency AgTaO3 samples were active till 580 nm, which correlates well with
of the photocatalytic process. The photogenerated electrons might stronger Vis absorption of those samples, probably resulting from the co-
migrate from the CB semiconductor via GQDs to adsorbed oxygen, presence of metallic silver. It is worth to mention that in case of pristine
forming O●-2 radicals responsible for pollutants’ oxidation. Furthermore, SrTiO3 and AgTaO3, slight Vis activity was also noticed, i.e., in range
the graphene and carbon QDs might couple with SrTiO3, SrSnO3, from 400 to 460 nm for SrTiO3, and from 400 to 480 nm for AgTaO3. The
AgTaO3, and thus also enhance the absorption of the semiconductor in similar Vis activity has already been reported for other Vis-inactive
the range of visible light, due to the electronic coupling between states semiconductors, e.g., titania [80], which could result either from im
of the graphite-essential GQDs/CQDs and conduction band states of purities or the oxygen vacancies. In case of pristine AgTaO3, the pho
semiconductor. Next, GQDs/CQDs can act as an electron reservoir to toactivity in the visible range of irradiation, might come also from the
11
Fig. 12. Photoluminescence emission spectra of pristine and of pristine and modified samples: (a) SrTiO3; (b) AgTaO3; (c) SrSnO3.
presence of metallic silver and silver nanoparticles (NPs), which typi

cally show absorption at around 420–500 nm (depending on the size and
shape), due to the localized surface plasmon resonance LSPR [81–84]. It
was found that the AgTaO3_GQDs_Er sample exhibited the highest Vis
photoabsorption among other samples, probably due to the synergistic
effect of co-presence of GQDs, Er and metallic silver. Moreover, the
content of Ag in this sample (3.71 at.%) was lower than that in pristine
AgTaO3 what is in line with results by Wei et al., who reported the
highest Vis photoabsorption for the sample with the lowest content of
silver [85]. According to the literature, it is well known that the prop
erties of silver NPs influence the position and shape of LSPR peak. It was
reported that the broader LSPR is, the higher is the photoactivity of the
sample due to the efficient use of all emitted photons [85–87]. Conse
quently, it has been thought that AgTaO3_GQDs_Er sample demonstrates
the highest Vis photoactivity. It is proposed that some silver NPs might
be formed during the synthesis process, as confirmed by DRS shape
(Fig. 14c) and XPS analysis (Table 2, Fig. 8). However, the XRD mea
surements did not revealed the presence of the metallic silver, probably
due to low content of silver and the overlapping of the silver peaks with
those corresponding to AgTaO3 (Fig. 4c). The broad silver LSPR peak
Fig. 13. Efficiency of toluene degradation as the function of Vis LEDs irradia
tion time over pristine and modified: SrSnO3; SrTiO3; AgTaO3. indicates the variety in the size and the shape of silver nanoparticles. Ma
et al. noted that silver NPs cause significant changes to the absorption
spectrum of TiO2 resulting in high absorbance from 400 nm to entire
visible region, which is characteristic for LSPR absorption of spatially
confined electrons in Ag NPs [81,88]. SrTiO3 and SrSnO3 photocatalysts
12
Fig. 14. Action spectra for the photocatalytic degradation of phenol in the presence of pristine and modified samples (a) SrTiO3; (b) AgTaO3; (c) SrSnO3 (the lines
represent UV-Vis spectra, the dots represents AQE).
were active till 540 nm and AgTaO3 till 580 nm, and thus it might be caused by the method of preparation, are observed by the crystalline
concluded that although all photocatalysts might absorb light at much properties and type of hybridization, i.e., GQDs are composed mainly of
longer wavelengths, those absorption do not result in photocatalyst sp2 hybridized carbon and they are well crystallized, whereas CQDs
activation or the concentrations of the phenol by-products are below the possess mainly sp3 hybridized carbon and they are usually amorphous
detection limit. [91]. Accordingly, it is expected that the mobility of charge carriers (i.e.,
To sum up, the obtained perovskites (SrTiO3, SrSnO3 and AgTaO3) electrons) is much higher on well-crystallized GQDs than that on CQDs,
are the wide bandgap semiconductors with bandgap >3.0 eV (SrTiO3 – and thus resulting in efficient electron transfer to adsorbed reagents on
3.2 eV, SrSnO3 – 3.4 eV and AgTaO3 – 3.4 eV), and thus exhibit super the photocatalyst surface. Confirmation of this thesis is the higher
lative properties only under UV irradiation. It was proved (by phenol photocatalytic activity (both in the water and gas phase – phenol and
and toluene photodegradation) that modification by graphene/carbon toluene photodegradation) for semiconductors modified with GQDs
QDs and erbium caused enhanced photocatalytic properties also under than for those modified by CQDs. Moreover, the enhanced photo
visible range of irradiation (λ > 400 nm). Describing in detail, the catalytic activity was caused by the addition of erbium. In this case, the
photocatalytic reaction is initiated after capturing of sunlight by a excitation under visible irradiation was attributed to both the presence
semiconductor. Consequently, electrons can transfer from valence band of carbon in a form of QDs as well as modification with erbium.
(VB) to conduction band (CB) leaving behind holes in the VB. If the
photogenerated e- — h+ pairs’ separation is maintained, the photo 3.2.8. Antimicrobial properties
generated carriers can move to the semiconductor surfaces [1,89,90]. The procedure for determining biocidal activity is shown schemati
Then, the oxygen species are formed and the pollutants present on the cally in the Fig. 1 (Experimental Part). Considering the low bactericidal
catalyst surface are decomposed. In this regard, QDs act as an electron activity of Sr [92,93], the activities of QDs-modified/unmodified SrSnO3
acceptor from the semiconductor’s conduction band (CB) and the re (Fig. 15a) and SrTiO3 (Fig. 15b) could be recognized by intrinsic activity
action center. Firstly, the coupling of GQDs/CQDs with SrTiO3, SrSnO3 of oxides and/or photocatalytic activity of the sample. In addition, in the
or AgTaO3 enhanced the absorption of perovskites in the range of visible case of SrTiO3, it was found that the modification with GQDs_Er did not
light, probably due to the electronic coupling between states of the enhance the bactericidal activity in the dark (Fig. 15b). As shown in
graphite-essential QDs (or CQDs) and conduction band states of semi Fig. 15a, pristine SrSnO3 exhibits the activity under Vis. It was also
conductors. Secondly, QDs probably can act as an electron reservoir to found that the modification with GQDs enhanced the bactericidal ac
trap photogenerated electrons from semiconductors and promote the tivity, although it has been proposed that GQD itself possessed low
separation of photogenerated electron-holepairs (which is supported by toxicity [27]. Importantly, although intrinsic (dark) activity of SrSnO3
PL measurement) [79]. The differences between GQDs and CQDs, was not observed, the combination of SrSnO3 and GQDs could facilitate
13
Fig. 15. Antimicrobial properties of pristine and modified samples after 180 min of irradiation and in the dark: (a) SrSnO3; (b) SrTiO3; (c) AgTaO3 and (d) AgTaO3
after 30 min of irradiation and in the dark.
the response in the dark. The bactericidal activity of SrTiO3 and AgTaO3 jagged surface, SnSrO3 formed rods, whereas AgTaO3 were faceted.
GQDs were strongly enhanced by the visible light irradiation, due to the Although modification of the perovskites by quantum dots lowered their
photocatalytic biocidal action (Fig. 15b), since it has been proposed that specific surface area, it also resulted in decreased photoluminescence
the visible-light (>420 nm) irradiation itself did not show the bacteri intensity, suggesting the impeded charge carriers’ recombination. The
cidal activity [94]. Moreover, although the silver itself strongly lowest photoluminescence intensity was observed for the samples
contributed to the bactericidal activity, it is clear that the modification modified by graphene quantum dots and erbium. The higher photo
with GQDs enhanced the activity both under Vis and dark condition catalytic performance of the modified samples was confirmed by the
(Fig. 15c and d). Some reports also suggested that the bactericidal ac photocatalytic tests performed under visible-light irradiation for phenol
tivity of silver-modified semiconductors (mainly titania) was due to the photodegradation in the aqueous phase (estimated apparent quantum
intrinsic activity of silver and photocatalytic reaction (reactive oxygen efficiency) and toluene decomposition in the gas phase. The mentioned
species) under visible-light irradiation [87,94–98]. Therefore, it is pro samples exhibited the highest photocatalytic activity in both analysed
posed that the enhanced activity of AgTaO3 under Vis might be due to reaction systems as compared with those modified with carbon quantum
the plasmonic photocatalysis (Fig. 14c) [99]. Importantly, it has been dots and the pristine samples (the lowest activity). In this regard, the
reported that titania modified with carbon, and both with graphene and excitation phenomenon under visible light was attributed to both the
carbon did not show the difference in the bactericidal activity, and thus, presence of carbon in a form of QDs as well as modification with erbium.
the existence of graphene seemed not to be responsible for the anti The higher photocatalytic activity of the perovskites containing gra
bacterial activity [76]. However, in the case of present study, the dark phene QDs and erbium was probably caused by enhanced capturing of
activities of SrSnO3 and AgTaO3 were remarkably enhanced by the the excited electrons, resulting in reduced recombination of the
modification with GQDs, possibly due to the enhanced direct interaction electron-hole pairs, thus improving quantum efficiency. Although GQDs
between the photocatalyst and bacteria [100]. In this sense, a possible belong also to carbon QDs, and thus having similar properties to other
reason of the less enhancement of bactericidal activity of SrTiO3 by CQDs, such as opto-electronic properties, toxicity, solubility and good
GQDs in the dark could result from the less carbon content, as shown in photostability, the differences, caused by the method of preparation, are
Table 2. Summarizing, all GQDs-modified samples showed higher ac observed by the size, crystalline properties and type of hybridization. As
tivity than unmodified ones under Vis, possibly due to the enhanced a result, the mobility of charge carriers (i.e., electrons) should be much
interaction with bacteria and the co-existence of GQDs and H2O2 (which higher on well-crystallized GQDs than that on CQDs, which resulted in a
might be generated through photocatalytic oxidation of oxygen) [27]. higher photocatalytic activity.
Taking into account the type of the perovskites, the highest photo
4. Conclusions activity under Vis irradiation was observed for the AgTaO3_GQDs_Er
sample, probably due to the synergistic effect between GQDs, erbium
The strontium titanate, silver tantalite and strontium stannate pe and metallic silver.
rovskites were successfully synthesised via solvothermal route at 180 ◦ C. The antimicrobial activity against Escherichia coli K12 bacteria
The as-prepared samples were modified with carbon quantum dots or confirmed that the co-presence of GQDs and Er resulted in the highest
graphene quantum dots with 0.5 mol.% of erbium. The morphology activity. It is expected that the co-existence of GQDs and generated
analysis showed that the SrTiO3 particles had spherical shape with reactive oxygen species (e.g., H2O2) could participate in the overall
14
antimicrobial action. Moreover, it was found that GQDs also possessed sensitization of TiO2: Simultaneous decolorization of dyes and production of
oxidizing radicals, Appl. Catal. B 203 (2017) 475–484.
the bactericidal activity themselves.
[12] E.M. Samsudin, S.B.A. Hamid, J.C. Juan, W.J. Basirun, G. Centi, Enhancement of
It is thought that the data obtained might provide useful information the intrinsic photocatalytic activity of TiO2 in the degradation of 1,3,5-triazine
for designing new materials for the efficient removal of chemical and herbicides by doping with N F, Chem. Eng. J. 280 (2015) 330–343.
microbiological pollutants under visible irradiation. [13] Y. Park, N.J. Singh, K.S. Kim, T. Tachikawa, T. Majima, W. Choi, Fullerol-Titania
Charge-Transfer-Mediated Photocatalysis Working under Visible Light, Chem.
European J. 15 (2009) 10843–10850.
CRediT authorship contribution statement [14] R. Lamba, A. Umar, S.K. Mehta, S.K. Kansal, Enhanced visible light driven
photocatalytic application of Ag2O decorated ZnO nanorods heterostructures,
Sep. Purif. Technol. 183 (2017) 341–349.
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Dr Marta Paszkiewicz-Gawron gratefully acknowledge financial S. Galdiero, L. Lombardi, A. Falanga, An integrated study on antimicrobial
activity and ecotoxicity of quantum dots and quantum dots coated with the
support for the research fellowship at Hokkaido University, Institute for
antimicrobial peptide indolicidin, Int. J. Nanomed. 2016 (11) (2016) 4199–4211.
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Applied Surface Science 541 (2021) 148425

Contents lists available at ScienceDirect

Applied Surface Science

Stannates, titanates and tantalates modified with carbon and graphene

1. Introduction photocatalysts for degradation of pollutants as well as for the hydrogen

Fig. 1. Scheme of antibacterial assay against E. coli procedure.

SrTiO3 – 84 3.8990 3.8990 59.273 107.9

SrTiO3 – – 21.24 13.76 – 52.00 – 13.00 <0.1

presence of metallic silver and silver nanoparticles (NPs), which typi

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Applied Surface Science 541 (2021) 148425

Contents lists available at ScienceDirect

Applied Surface Science

Stannates, titanates and tantalates modified with carbon and graphene

1. Introduction photocatalysts for degradation of pollutants as well as for the hydrogen

Fig. 1. Scheme of antibacterial assay against E. coli procedure.

SrTiO3 – 84 3.8990 3.8990 59.273 107.9

SrTiO3 – – 21.24 13.76 – 52.00 – 13.00 <0.1

presence of metallic silver and silver nanoparticles (NPs), which typi­

You might also like

presence of metallic silver and silver nanoparticles (NPs), which typi